Adsorption of hazardous and noxious 4-nitrophenol by a silsesquioxane organic-inorganic hybrid material

Journal of Sol-Gel Science and Technology - This paper reports the synthesis and characterization of a silsesquioxane polymer based on a rigid silica inorganic core and...     

Comprehensive two-dimensional liquid chromatography-based quali-quantitative screening of aqueous phases from pyrolysis bio-oils

Pyrolysis processes are an alternative to minimize the environmental problem associated to agrifood industrial wastes. The main product resulting from these processes is a high-value liquid product, called bio-oil. Recently, the use of comprehensive two-dimensional liquid chromatography (LC × LC) has been demonstrated as a useful tool to improve the characterization of the water-soluble phases of bio-oils, considering their complexity and high water content. However, the precise composition of bio-oils from different agrifood byproducts is still unknown. In the present study, the qualitative and quantitative screening of eight aqueous phases from different biomasses, not yet reported in the literature, using LC × LC is presented. The two-dimensional approach was based on the use of two reverse phase separations. An amide column in the first dimension together with a C18 column in the second dimension were employed. Thanks to the use of diode array and mass spectrometry detection, 28 compounds were identified and quantified in the aqueous phase samples with good figures of merit. Samples showed a distinct quali-quantitative composition and a great predominance of compounds belonging to aldehydes, ketones and phenols, most of them with high polarity.     

Microfluidic Setup for Simultaneous Separation and Electrochemical Determination of Hg2+ and Ag+ Ions in Water

Here is presented a setup made of a combination of an injection valve, a hand-made chromatographic microcolumn and an electrochemical detector for the simultaneous separation of Hg²⁺ and Ag⁺ ions in water. The microcolumns were packed with exchanger resin and used for the separation of Hg²⁺ and Ag⁺ ions, whereas a screen-printed carbon electrode (SPCE) was the amperometric detector. The performances of the SPCE towards ions were firstly studied in a FIA setup. The efficiency of ion separation was then evaluated. The reproducibility, stability, and the regeneration of the obtained microcolumns were also studied and discussed.     

Ionization of 2- and 4(5)-Nitroimidazoles Radiosensitizers: A “Kinetic Competition” Between NO2 and NO Losses

Nitroimidazoles are a class of chemicals with a remarkable broad spectrum of applications from the production of explosives to the use as radiosensitizers in radiotherapy. The understanding of thedynamics of their fragmentation induced by ionizing sources is of fundamental interest. The goal of this work is to theoretically investigate the kinetic competition between the two most important decomposition channels of 2, 4 and 5-Nitroimidazole cations: the NO and NO₂ losses. The calculated rate constants of the two processes are in very good agreement with the experimental Photoelectron-Photoion Coincidence (PEPICO) branching ratio. This study solves the intriguing and theoretically unexplained experimental observation that 2-Nitroimidazole, at variance with the other two regio-isomers is a source for only NO at low energies (<12.76 eV). This is a key point for biomedical application of the nitroimidazoles, because NO is the vasodilator that favors the reoxigenation of hypoxic tumor tissues.     

Direct thermal extraction and gas chromatographic-mass spectrometric determination of volatile compounds of extra-virgin olive oils

The instrumental performances of a Thermo Desorption-Cooled Injection System coupled with a gas chromatography-mass spectrometer (GC-MS) were improved by a Plackett-Burman experimental design for the direct thermal extraction of volatile compounds from extra-virgin olive oils. The obtained experimental conditions were applied to the analysis of samples from West Liguria (cv. Taggiasca > or = 90%) and Spain (cv. Arbequina), which shared such similar sensorial features that Taste Panel did not distinguish them. Principal component analysis (PCA) was then applied to the experimental data. Three linear combinations of the amounts of the lipoxygenase oxidation products proved to be decisive and sufficient in the differentiation of the two groups of samples.     

Fabrication,chemical modification,and topographical patterning of reactive gels assembled from azlactone‐functionalized polymers and a diamine

The work reported here demonstrates an approach to the fabrication of chemically reactive and topographically patterned hydrogels using the azlactone‐functionalized polymer poly(2‐vinyl‐4,4'‐dimethylazlactone) (PVDMA) and the hydrophilic diamine Jeffamine®. Gels were initially assembled in DMSO but can be subsequently transferred into aqueous media to form hydrogels. Spectroscopic characterization of assembled gels demonstrated that variation in the stoichiometric ratio of azlactones to amines during gel synthesis permits control over the extent of crosslinking in the gels. Residual azlactones not consumed during crosslinking can be exploited to further functionalize these gels with hydrophobic, hydrophilic, and macromolecular amines that influence the physicochemical properties of these materials in aqueous solvents. The surface and bulk of these gels can be differentially functionalized (i.e., different functional groups on the gel surface relative to the bulk) by taking advantage of different rates of diffusion of macromolecular amines versus small molecule amines into assembled gels. Finally, these azlactone‐functionalized gels can be topographically patterned with microwell arrays using a replica molding technique and chemically modified postfabrication with amine nucleophiles. This reactive approach to the fabrication of topographically patterned and chemically functionalized hydrogels offers a straightforward method for the rapid synthesis of micropatterned scaffolds of interest in a broad range of applications. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3185–3194     

Coordination of metal ions by indolic acids. Complexes of indole-3-carboxylic,indole-3-acetic,indole-3-β-acrylic,indole-N-acetic and indole-N-methyl-2-carboxylic acids with some divalent metal ions

Complexes of formula M(L)₂·nH₂O [M=Co or Ni; L=indole-3-carboxylic (I3CH), indole-3-acetic (I3AH), indole-N-acetic (INAH), indole-N-methyl-2-carboxylic (INMH) and M=Co or Ni and Cu, L=indole-3-β-acrylic acids (I3βH)] were pepared and characaterized by i.r. and electronic spectroscopy and by susceptibility measurements and e.s.r. at room and low temperature. The cobalt and nickel complexes exhibit a distorted octahedral coordination except the Co(I3C)₂ complex for which a tetrahedral coordination was suggested. The Cu(I3β)₂·H₂O shows e.p.r. features that can be interpreted if the triplet state, S=1, depending on the temperature, is able to migrate through the crystal lattice of carboxylate dimers such as the copper(II) acetate monohydrate.     

Intramolecular nitrilimine cycloadditions onto β-lactams bearing an alkenyl dipolarophile: synthesis of novel tricyclic β-lactams

A five-step synthesis of novel tricyclic β-lactams has been exploited by stereoselective intramolecular cycloadditions of appropriate nitrilimines 6 and 12. These labile intermediates were generated in situ from the corresponding hydrazonoyl chlorides giving rise to the hitherto unknown azeto[3′,4′:1,2]hexano[3,4-c]pyrazole and azeto[3′,4′:1,2]heptano[3,4-c]pyrazole skeletons.